Novel graphene-like boron nitride(BN)/Bi_(3)O_(4)Br photocatalysts have been controllably synthesized through a facile solvothermal method for the first time. Layer contact stacking between graphene-like BN and ultrat...Novel graphene-like boron nitride(BN)/Bi_(3)O_(4)Br photocatalysts have been controllably synthesized through a facile solvothermal method for the first time. Layer contact stacking between graphene-like BN and ultrathin Bi_(3)O_(4)Br was achieved with strong interaction. Dehalogenation is designed to harvest more visible light, and the ultrathin structure of Bi_(3)O_(4)Br is designed to accelerate charge transfer from inside to the surface. After graphene-like BN was engineered, photocatalytic performance greatly improved under visible light irradiation. Graphene-like BN can act as a surface electron-withdrawing center and adsorption center, facilitating molecular oxygen activation. O_(2)^(·-)was determined to be the main active species during the degradation process through analyses of electron spin resonance and XPS valence band spectra.展开更多
To improve the photocatalytic oxidation reaction activity for NO removal, photocatalysts with excellent activity are required to activate molecular oxygen. Solid solution and heterojunction were suggested as effective...To improve the photocatalytic oxidation reaction activity for NO removal, photocatalysts with excellent activity are required to activate molecular oxygen. Solid solution and heterojunction were suggested as effective strategies to enhance the molecular oxygen activation viaexciton and carrier photocatalysis. In this study, a solid solution and heterojunction containing BiOBr0.5I0.5/BiOI catalyst was synthesized, and it showed improved photocatalytic activity for removing NO. The photocatalytic NO removal mechanism indicated that synergistic effects between the solid solution and heterojunction induced the enhanced activity for molecular oxygen activation. The photogenerated holes, superoxide, and singlet oxygen generated by the carrier and exciton photocatalysis supported the high photocatalytic NO removal efficiency. This study provides new ideas for designing efficient Bi-O-X(X = Cl, Br, I) photocatalysts for oxidation reactions.展开更多
Tuning the coordination environment is the research axis of single atom catalysts (SACs). SACs are commonly stabilized by various defects from support. Here, we report a lattice confined Pd SAC using MnO_(2) as suppor...Tuning the coordination environment is the research axis of single atom catalysts (SACs). SACs are commonly stabilized by various defects from support. Here, we report a lattice confined Pd SAC using MnO_(2) as support. Compared with the Pd clusters anchored on the surface, the lattice confined Pd single atoms allows spontaneous exaction of surrounding lattice oxygen at room temperature when employed in CO oxidation. The MnO_(2) supported Pd SAC exhibited a high turnover frequency of 0.203 s^(−1) at low reaction temperature, which is higher than that of recently reported Pd SACs. Theoretical calculations also confirmed the confined monatomic Pd activate lattice oxygen with an ultralow energy barrier. Our results illustrate that the unique coordination environment of single atom provided by lattice confinement is promising to boost the activity of SACs.展开更多
In this work,the tunable introduction of oxygen vacancies in bismuth tungstate was realized via asimple solvothermal method with the assistance of iodine doping.With the predictions afforded bytheoretical calculations...In this work,the tunable introduction of oxygen vacancies in bismuth tungstate was realized via asimple solvothermal method with the assistance of iodine doping.With the predictions afforded bytheoretical calculations,the as-prepared bismuth tungstate was characterized using various tech-niques,such as X-ray diffraction,Raman spectroscopy,scanning electron microscopy,transmissionelectron microscopy,X-ray photoelectron spectroscopy,electron spin resonance spectroscopy,anduV-Vis diffuse reflectance spectroscopy.The different concentrations of the oxygen vacancies onbismuth tungstate were found to be intensely correlated with iodine doping,which weakened thelattice oxygen bonds.Owing to the sufficient oxygen vacancies introduced in bismuth tungstate as aresult of iodine doping,the molecular oxygen activation was remarkably enhanced,thus endowingbismuth tungstate with high activity for the photocatalytic degradation of sodium pentachloro-phenate.More encouraging is the total organic carbon removal rate of sodium pentachlorophenateover iodine-doped bismuth tungstate that exceeded 90%in only 2 h and was 10.6 times higher thanthat of the pristine bismuth tungstate under visible light irradiation.Moreover,the mechanism,through which the degradation of sodium pentachlorophenate over iodine-doped bismuth tung-state is enhanced,was speculated based on the results of radical detection and capture experiments.This work provides a new perspective for the enhanced photocatalytic degradation of organochlo-rine pesticides from the oxygen vacancy-induced molecular oxygen activation over iodine-dopedbismuth tungstate.展开更多
Density functional theory calculations were carried out to investigate the influence of doping transition metal(TM) ions into the ceria surface on the activation of surface lattice oxygen atoms. For this purpose, the ...Density functional theory calculations were carried out to investigate the influence of doping transition metal(TM) ions into the ceria surface on the activation of surface lattice oxygen atoms. For this purpose, the structure and stability of the most stable(111) surface termination of CeO2 modified by TM ions was determined. Except for Zr and Pt dopants that preserve octahedral oxygen coordination, the TM dopants prefer a square-planar coordination when substituting the surface Ce ions. The surface construction from octahedral to square-planar is facile for all TM dopants, except for Pt(1.14 e V) and Zr(square-planar coordination unstable). Typically, the ionic radius of tetravalent TM cations is much smaller than that of Ce4+, resulting a significant tensile-strained lattice and explaining the lowered oxygen vacancy formation energy. Except for Zr, the square-planar structure is the preferred one when one oxygen vacancy is created. Thermodynamic analysis shows that TM-doped CeO2 surfaces contain oxygen defects under typical conditions of environmental catalysis. A case of practical importance is the facile lattice oxygen activation in Zr-doped CeO2(111), which benefits CO oxidation. The findings emphasize the origin of lattice oxygen activation and the preferred location of TM dopants in TM-ceria solid solution catalysts.展开更多
Piezoelectric semiconductors bear the bifunctional photocatalysis and piezocatalysis,while the absent or weak internal charge driving force severely restricts its catalytic activity.Developing polarization strategy is...Piezoelectric semiconductors bear the bifunctional photocatalysis and piezocatalysis,while the absent or weak internal charge driving force severely restricts its catalytic activity.Developing polarization strategy is desirable,and particularly understanding its mechanism from a microscopic perspective remains scanty.Herein,we report a secondary recrystallization approach to achieving the simultaneous micro-and macroscopic polarization enhancement on Bi2WO6 nanosheets for boosting piezo-photocatalytic oxygen activation,and unravel the mechanism at an atom-level.The secondary recrystallization process not only results in a strengthened distortion of[WO6]octahedra with distortion index enhancement by~20%for a single octahedron,but also enables lateral crystal growth of nanosheets along the ab plane(av.50 to 180 nm),which separately allows the rise in dipole moment of unit cell(e.g.,1.63 D increase along a axis)and the stacking of the distorted[WO6]octahedron to accumulate the unit cell dipole,collectively contributing to the considerably strengthened spontaneous polarization and piezoelectricity.Besides,exposure of large-area{001}front facet enables more efficient capture and conversion of stress into piezo-potential.Therefore,the well-recrystallized Bi2WO6 nanosheets exhibit considerably promoted piezo-photocatalytic reactive oxygen species generation,given the decreased specific surface area.This work presents a feasible methodology to regulate inside-out polarization for guiding carriers transfer behavior,and may advance the solid understanding on the intrinsic mechanism.展开更多
Using a ditopic organic linker 4-(1H-pyrazol-4-yl)benzoic acid(H_(2)pba),FICN-6,a metal-organic framework containing both Cu_(2)(O_(2)CR)_(4)and Cu_(3)(OH)(pyz)_(3)(O_(2)CR)secondary building units(SBUs),was synthesiz...Using a ditopic organic linker 4-(1H-pyrazol-4-yl)benzoic acid(H_(2)pba),FICN-6,a metal-organic framework containing both Cu_(2)(O_(2)CR)_(4)and Cu_(3)(OH)(pyz)_(3)(O_(2)CR)secondary building units(SBUs),was synthesized.FICN-6 adopts in an unusual intercatenated structure with SBUs from two distinct networks connecting to each other.Presence of Cu_(3)clusters makes FICN-6 a good heterogeneous catalyst for oxygen activation and aerobic oxidative C-C coupling of organic boronic acids.展开更多
Selective aerobic oxidation of alcohols under mild conditions is of great importance yet challenging,with the activation of molecular oxygen(O2)as a crucial capability of the catalysts.Herein,we demonstrate that an Al...Selective aerobic oxidation of alcohols under mild conditions is of great importance yet challenging,with the activation of molecular oxygen(O2)as a crucial capability of the catalysts.Herein,we demonstrate that an Al2O3-supported Pd single-atom catalyst leads to higher activity and selectivity compared to Pd nanoparticles for the oxidation of cinnamyl alcohol.The Al2O3 support used in this study is rich in coordinately unsaturated Al3+sites,which are apt for binding to Pd atoms through oxygen bridges and present a distinct metal-support interaction(MSI).The suitable MSI then leads to a unique electronic characteristic of the Pd single atoms,which can be confirmed via X-ray photoelectron spectroscopy,normalized X-ray absorption near-edge structure,and diffuse reflectance Fourier transform infrared spectroscopy.Moreover,this unique electronic state is proposed to be responsible for its high catalytic activity.With the help of in-situ UV-vis spectra and electron spin resonance spectra,a specific alcohol oxidation route with O2 activation mechanism is then identified.Active oxygen species behaving chemically like singlet-O2 are generated from the interaction of O2 with Pd1/Al2O3,and then oxidize the partially dehydrogenated intermediates produced by the adsorbed allylic alcohols and Pd atoms to the desired alkenyl aldehyde.This work provides a promising path for the design and development of high-activity catalysts for aerobic oxidation reactions.展开更多
Largely limited by the high dissociation energy of the O—O bond,the photocatalytic molecular oxygen activation is highly challenged,which re strains the application of photocatalytic oxidation technology for atmosphe...Largely limited by the high dissociation energy of the O—O bond,the photocatalytic molecular oxygen activation is highly challenged,which re strains the application of photocatalytic oxidation technology for atmospheric pollutants removal.Herein,we design and fabricate the InP QDs/g-C_(3)N_(4) compounds.The introduction of InP QDs promotes the charge transfer within the interface resulting in the effective separation of photo-generated carriers.Furthermore,InP QDs greatly facilitates the activation of molecular oxygen and promote the formation of O_(2)·under visible-light illuminatio n.These conclusions are identified by experimental and calculation results.Hence,NO can be combined with the O_(2)·to form O—O—N—O intermediate to direct conversion into NO_(3).As a result,the NO removal ratio of g-C_(3)N_(4) has a one fold increase after InP QDs loaded and the generation of NO_(2) is effectively inhibited.This wo rk may provide a strategy to design highly efficient materials for molecular oxygen activation.展开更多
Sunlight-driven activation of molecular oxygen(O_(2))for organic oxidation reactions offers an appealing strategy to cut down the reliance on fossil fuels in chemical industry,yet it remains a great challenge to simul...Sunlight-driven activation of molecular oxygen(O_(2))for organic oxidation reactions offers an appealing strategy to cut down the reliance on fossil fuels in chemical industry,yet it remains a great challenge to simultaneously tailor the charge kinetics and promote reactant chemisorption on semiconductor catalysts for enhanced photocatalytic performance.Herein,we report iron sites immobilized on defective BiOBr nanosheets as an efficient and selective photocatalyst for activation of O_(2) to singlet oxygen(^(1)O_(2)).These Fe^(3+) species anchored by oxygen vacancies can not only facilitate the separation and migration of photogenerated charge carrier,but also serve as active sites for effective adsorption of 02.Moreover,low-temperature phosphorescence spectra combined with X-ray photoelectron spectroscopy(XPS)and electronic paramagnetic resonance(EPR)spectra under illumination reveal that the Fe species can boost the quantum yield of excited triplet state and accelerate the energy transfer from excited triplet state to adsorbed O2 via a chemical loop of Fe^(3+)/Fe^(2+),thereby achieving highly efficient and selective generation of ^(1)O_(2).As a result,the versatile iron sites on defective BiOBr nanosheets contributes to near-unity conversion rate and selectivity in both aerobic oxidative coupling of amines to imines and sulfoxidation of organic sulfides.This work highlights the significant role of metal sites anchored on semiconductors in regulating the charge/energy transfer during the heterogeneous photocatalytic process,and provides a new angle for designing high-performance photocatalysts.展开更多
In recent decade, Au nanoclusters of atomic precision （AunLm, where L= organic ligand： thiolate andphosphine） have been shown as a new promising nanogold catalyst. The well-defined AunLm catalystspossess unique ele...In recent decade, Au nanoclusters of atomic precision （AunLm, where L= organic ligand： thiolate andphosphine） have been shown as a new promising nanogold catalyst. The well-defined AunLm catalystspossess unique electronic properties and frameworks, providing an excellent opportunity to correlate theintrinsic catalytic behavior with the cluster＇s framework as well as to study the catalytic mechanismsover gold nanoclusters. In this review, we only demonstrate the important roles of the gold nanoclustersin the oxygen activation （e.g., 302 to 102） and their selective oxidations in the presence of oxygen （e.g., COto C02, sulfides to sulfoxides, alcohol to aldehyde, styrene to styrene epoxide, amines to imines, andglucose to gluconic acid）. The size-specificity （Au25 （1.3 nm）, Au38 （].5 nm）, Au144 （1.9 nm）, etc.）, ligandengineering （e.g., aromatic vs aliphatic）, and doping effects （e.g., copper, silver, palladium, and platinum）are discussed in details. Finally, the proposed reactions＇ mechanism and the relationships of clusters＇structure and activity at the atomic level also are presented.展开更多
Cobalt-rich perovskite oxides play a paramount role in catalyzing oxygen evolution reaction(OER)on account of their acceptable intrinsic activity but are still challenging due to the high costs and undesired stability...Cobalt-rich perovskite oxides play a paramount role in catalyzing oxygen evolution reaction(OER)on account of their acceptable intrinsic activity but are still challenging due to the high costs and undesired stability.In response to the defects,herein,the Mg-incorporated perovskite cobaltite SrCo_(0.6)Fe_(0.3M)g_(0.1)O_(3-δ)(SCFM-0.1)is proposed as a novel earth-abundant and durable OER electrocatalyst.A well-consolidated cubic-symmetry structure and more active oxygen intermediates are enabled upon Mg substitution.Hence,the optimized SCFM-0.1 perovskite oxide achieves prominent OER electrocatalytic performance,that is,a low overpotential of only 320 mV at 10 mA cm^(-2),a small Tafel slope of 65 mV dec^(-1),as well as an outstanding durability within 20 h,substantially outperforming that of the pristine SrCo_(0.7)Fe_(0.3)O_(3-δ)and benchmark Ba_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3-δ)and IrO_(2) catalysts.The strong pHdependent behavior associated with lattice oxygen activation mechanism for SCFM-0.1 catalyst is also confirmed.This work paves a unique avenue to develop cost-effective and robust perovskite cobaltites for efficient OER electrocatalysis.展开更多
<img src="Edit_bdc7d851-e537-40df-990c-d678defa9648.png" alt="" />(M = Au, Ag, Cu;<span lang="EN-US" style="font-size:9pt;font-family:"color:black;"><i>n&...<img src="Edit_bdc7d851-e537-40df-990c-d678defa9648.png" alt="" />(M = Au, Ag, Cu;<span lang="EN-US" style="font-size:9pt;font-family:"color:black;"><i>n</i></span>= 1, 2, 3) clusters were used as a cluster model to study the activation of oxygen molecules on single-atom catalysts. Structures of <img src="Edit_bb84deb7-e24a-4777-a2f6-a1621ddd2afc.png" alt="" /> clusters were studied by density functional calculations with global optimization. For each <span style="font-family:"color:black;white-space:normal;"><i>n</i></span>, the most stable structures are quite similar for different metal types, and the oxygen molecule prefers to be adsorbed onto M atoms. It is found that the activation degree of oxygen is higher on clusters with non-noble metal Cu than that of Ag or Au containing clusters, by comparing the changes of O-O bond length and vibrational frequency, natural charge population analysis, Fuzzy bond order analysis, and energy barriers of O<sub>2</sub> dissociation. CO oxidation was used as a probe reaction to study the reactivity of Cu-containing clusters, and it is found that the reactivity decreases with the increase of the size of silicon-oxygen clusters. Our results give a new aspect to understand the reaction mechanism of non-precious metal single-atom catalyst for oxygen activation with high efficiency.展开更多
Metal-based perovskite oxides have contributed significantly to the advanced oxidation processes(AOPs)due to their diverse active sites and excellent compositional/structural flexibility.In this study,we specially des...Metal-based perovskite oxides have contributed significantly to the advanced oxidation processes(AOPs)due to their diverse active sites and excellent compositional/structural flexibility.In this study,we specially designed a perovskite oxide with abundant oxygen vacancies,SrCo_(0.8)Fe_(0.2)O_(3)(SCF),and firstly applied it as a catalyst in peroxymonosulfate(PMS) activation towards organic pollutants degradation.The result revealed that the prepared SCF catalyst exhibited excellent performance on organic compounds degradation.Besides,SCF showed much better activity than La_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3)(LSCF) in terms of reaction rate and stability for the degradation of the organic compounds.Based on the analysis of scanning electron microscope,transmission electron microscope,X-ray diffraction,N_(2) adsorption-desorption,X-ray photoelectron spectroscopy and electron paramagnetic resonance,it was confirmed that the perovskite catalysts with high content of Sr doping at A-site could effectively create a defect-rich surface and optimize its physicochemical properties,which was responsible for the excellent heterogeneous catalytic activity of SCF.SCF can generate three highly active species:~1 O_(2),SO_(4)^(-)· and ·OH in PMS activation,revealing the degradation process of organic compounds was a coupled multiple active species in both radical and nonradical pathway.Moreover,it was mainly in a radical pathway in the degradation through PMS activation on SCF and SO_(4)^(-)· radicals produced were the dominant species in SCF/PMS system.This study demonstrated that perovskite-type catalysts could enrich OVs efficiently by doping strategy and regulate the PMS activation towards sulfate radical-based AOPs.展开更多
The function-led design of porous hydrochar from mineral-rich biowaste for environmental applications inevitably suffers from carbon-ash recalcitrance.However,a method to alter the original carbon skeleton with ash re...The function-led design of porous hydrochar from mineral-rich biowaste for environmental applications inevitably suffers from carbon-ash recalcitrance.However,a method to alter the original carbon skeleton with ash remains elusive and hinders the availability of hydrochar.Herein,we propose a facile strategy for breaking the rigid structure of carbon-ash coupled hydrochar using phase-tunable molten carbonates.A case system was designed in which livestock manure and NaHCO3 were used to prepare the activated hydrochar,and NH3 served as the target contaminant.Due to the redox effect,we found that organic fractions significantly advanced the melting temperature of Na2CO3 below 800℃.The Na species steadily broke the carbon-ash interaction as the thermal intensity increased and transformed inorganic constituents to facilitate ash dissolution,rebuilding the hydrochar skeleton with abundant hierarchical channels and active defect edges.The surface polarity and mesopore distribution collectively governed the five cycles NH3 adsorption attenuation process.Manure hydrochar delivered favorable potential for application with a maximum overall adsorption capacity of 100.49 mg·g^(-1).Integrated spectroscopic characterization and theoretical computations revealed that incorporating NH3 on the carbon surface could transfer electrons to chemisorbed oxygen,which promoted the oxidation of pyridine-N during adsorption.This work offers deep insight into the structure function correlation of hydrochar and inspires a more rational design of engineered hydrochar from high-ash biowaste.展开更多
During the course of mungbean (Phaseolus radiatus L.) germination, the rate of ethylene production and the activity of ACC synthase (1_aminocyclopropane_1_carboxylic acid synthase, EC4.4.1.4) began to increase in the ...During the course of mungbean (Phaseolus radiatus L.) germination, the rate of ethylene production and the activity of ACC synthase (1_aminocyclopropane_1_carboxylic acid synthase, EC4.4.1.4) began to increase in the 5th day of germination, and reached its peak in the 10th day and then decreased. The ethylene production and the activity of ACC synthase were obviously promoted by 10 μmol/L exogenous IAA (indole_3_acetic acid). The production of superoxide radical (O -· 2) and hydrogen peroxide (H 2O 2) were also promoted by exogenous IAA, suggesting that there was some relationship between active oxygen production and the activity of ACC synthase induced by exogenous IAA. The production of ethylene and the activity of ACC synthase increased dramatically when the seedlings were treated with exogenous O -· 2, whereas the exogenous H 2O 2 had no effects on the production of ethylene and the activity of ACC synthase. Exogenous SOD (superoxide dismutase, one scavenger of O -· 2) could inhibit the production of ethylene and the activity of ACC synthase, but exogenous CAT (catalase) could not. So it was possible that IAA would stimulate the activity of ACC synthase by inducing the production of O -· 2 in germinating mungbean seedlings, and this might be one of the regulating mechanism of ethylene synthesis in higher plants; the production of H 2O 2 induced by IAA was not the cause of the increase of the activity of ACC synthase and the production of ethylene.展开更多
In order to understand the role of active oxygen species in mediating plant injuries induced by far-UV radiation, seedlings of Taxus cuspidata Sieb. et Zucc. were irradiated by far-UV rays in laboratory for 4 weeks. T...In order to understand the role of active oxygen species in mediating plant injuries induced by far-UV radiation, seedlings of Taxus cuspidata Sieb. et Zucc. were irradiated by far-UV rays in laboratory for 4 weeks. The production of organic free-radicals in detached needles, and the production of O-2(radical anion) and O-1(2) in isolated chloroplasts were detected weekly by electron spin resonance (ESR) to evaluate their relative importance. The results show that the cumulative effect of far-UV irradiation, is best indicated by the production of organic free radicals in the needles, O-2(radical anion) production in chloroplasts is the next. The enhancement of O-1(2) production in chloroplasts by the cumulative far-UV irradiation seems to be not so important as O-2(radical anion) in mediating injuries induced by, far-UV radiation because of its high background value.展开更多
[Objective] The research aimed to study the effects of 1-methylcyclopropene （1-MCP） and chitosan on active oxygen metabolism and quality of fresh-cut potato during storage. [Method] The fresh-cut potato slices were ...[Objective] The research aimed to study the effects of 1-methylcyclopropene （1-MCP） and chitosan on active oxygen metabolism and quality of fresh-cut potato during storage. [Method] The fresh-cut potato slices were respectively treated with 1- MCP （2 μl/L）, chitosan or 1-MCP ＋ chitosan. During the storage period, the contents of superoxide anion （02）, malondialdehyde （MDA）, hydrogen dioxide （H202） and Vita- min C （Vc）, the activities of polyphenol oxidase （PPO）, peroxydase （POD） and super- oxide dismutase （SOD） as well as the respiratory rate of the fresh-cut potatoes in all the treatments were determined every day. The fresh-cut potato slices treated without any reagents were used as control. [Result] 1-MCP Treated could significantly de- creased the respiratory rate, PPO activity and the accumulations of 02 , H202 and MDA, increased the activities of SOD and POD and slowed down Vc content reduc- tion. On the contrary, potato treated with chitosan significantly inhibited the POD activi- ty in fresh-cut potato. Compared with the control, the combination of 1-MCP and chi- tosan showed a little but not significant better effects on potato preservation. [Conclu- sion] 1-MCP Treated showed the best effects on potato preservation.展开更多
Peach fruits [Prumus persica （L.） Batsch, cv. Yuhuasanhao] were used as materials to investigate the changes of reactive oxygen species （ROS） and related enzymes in mitochondria respiration during storage and then...Peach fruits [Prumus persica （L.） Batsch, cv. Yuhuasanhao] were used as materials to investigate the changes of reactive oxygen species （ROS） and related enzymes in mitochondria respiration during storage and then their influence on senescence of harvested Peach fruits was studied. The results showed that low temperature （5℃） strongly inhibited the reduction of firmness and the increase in respiration rate. During storage at ambient temperature （20℃）, ROS had a cumulative process while malondialdehye （MDA） content continued to increase in associated with enhanced membrane lipid peroxidation. Lipoxygenase （LOX） activity was strongly inhibited under the low temperature condition. The activities of succinic dehydrogenase （SDH）, cytochrome C oxidase （CCO）, and Ca^2＋-ATPase declined to a certain extent at ambient temperature, while they showed higher activities at low temperature, which may be related to lower membrane lipid peroxidation at low temperature. Higher Ca^2＋ content at ambient temperature may be responsible for impairment of mitochondrial function, thus, leading to fruit senescence. The results showed that under low temperature condition, the low accumulation of ROS and the low level of membrane lipid peroxidation could maintain the function of mitochondria that would help to delay the senescence of peach fruits. These suggested a close relationship existed between ROS metabolism and mitochondrial respiration. It can be inferred that the low temperature helps to delay senescence of peach fruits via suppression of ROS and related enzymes, maintain better homeostasis of Ca^2＋ in mitochondria and thus better mitochondrial functions.展开更多
Pt-based nanoframes represent a class of promising catalysts towards oxygen reduction reaction. Herein, we, for the first time, successfully prepared Pt-Pd octahedral nanoframes with ultrathin ridges less than 2 nm in...Pt-based nanoframes represent a class of promising catalysts towards oxygen reduction reaction. Herein, we, for the first time, successfully prepared Pt-Pd octahedral nanoframes with ultrathin ridges less than 2 nm in thickness. The Pt-Pd octahedral nanoframes were obtained through site-selected deposition of Pt atoms onto the edge sites of Pd octahedral seeds, followed by selective removal of the Pd octahedral cores via chemical etching. Due to that a combination of three-dimensional opens geometrical structure and Pt-skin surface compositional structure, the Pt-Pd octahedral nanoframes/C catalyst shows a mass activity of 1.15 A/mgPt towards oxygen reduction reaction, 5.8 times enhancement in mass activity relative to commercial Pt/C catalyst （0.20 A/mgPt）. Moreover, even after 8000 cycles of accelerated durability test, the Pt-Pd octahedral nanoframes/C catalyst still exhibits a mass activity which is more than three times higher than that of pristine Pt/C catalyst.展开更多
基金financially supported by the Fundamental Research Funds for the Central Universities (No.30922010302)the Start-Up Grant from Nanjing University of Science and Technology (AE89991/397)。
文摘Novel graphene-like boron nitride(BN)/Bi_(3)O_(4)Br photocatalysts have been controllably synthesized through a facile solvothermal method for the first time. Layer contact stacking between graphene-like BN and ultrathin Bi_(3)O_(4)Br was achieved with strong interaction. Dehalogenation is designed to harvest more visible light, and the ultrathin structure of Bi_(3)O_(4)Br is designed to accelerate charge transfer from inside to the surface. After graphene-like BN was engineered, photocatalytic performance greatly improved under visible light irradiation. Graphene-like BN can act as a surface electron-withdrawing center and adsorption center, facilitating molecular oxygen activation. O_(2)^(·-)was determined to be the main active species during the degradation process through analyses of electron spin resonance and XPS valence band spectra.
文摘To improve the photocatalytic oxidation reaction activity for NO removal, photocatalysts with excellent activity are required to activate molecular oxygen. Solid solution and heterojunction were suggested as effective strategies to enhance the molecular oxygen activation viaexciton and carrier photocatalysis. In this study, a solid solution and heterojunction containing BiOBr0.5I0.5/BiOI catalyst was synthesized, and it showed improved photocatalytic activity for removing NO. The photocatalytic NO removal mechanism indicated that synergistic effects between the solid solution and heterojunction induced the enhanced activity for molecular oxygen activation. The photogenerated holes, superoxide, and singlet oxygen generated by the carrier and exciton photocatalysis supported the high photocatalytic NO removal efficiency. This study provides new ideas for designing efficient Bi-O-X(X = Cl, Br, I) photocatalysts for oxidation reactions.
基金X.Liao gratefully thanks the support from the National Natural Science Foundation of China(No.21706216)the Sichuan Science and Technology Program(2020YFG0162)+3 种基金the Young Scholar Project in Xihua University.X.Li acknowledges the support from the National Natural Science Foundation of China(No.21972163)the Fundamental Research Funds for the Central Universities and DHU Distinguished Young Professor Program,and the Development Fund for Shanghai Talents.Z.Jiang acknowledges financial support from the Joint Fund U1732267.M.Y.thanks the JSPS KAKENHI(No.JP 18H05517)JST-CREST for financial supports,and Riken SPring-8 for the approval of the SRXRD measurement(20190028)EXAFS studies were carried out at the BL14W1 beamline in the Shanghai Synchrotron Radiation Facility[63],Shanghai Institute of Applied Physics,China(16ssr-f00787).X.Liao gratefully thanks the useful discussion with Ya Wang and Yanmin Liu.
文摘Tuning the coordination environment is the research axis of single atom catalysts (SACs). SACs are commonly stabilized by various defects from support. Here, we report a lattice confined Pd SAC using MnO_(2) as support. Compared with the Pd clusters anchored on the surface, the lattice confined Pd single atoms allows spontaneous exaction of surrounding lattice oxygen at room temperature when employed in CO oxidation. The MnO_(2) supported Pd SAC exhibited a high turnover frequency of 0.203 s^(−1) at low reaction temperature, which is higher than that of recently reported Pd SACs. Theoretical calculations also confirmed the confined monatomic Pd activate lattice oxygen with an ultralow energy barrier. Our results illustrate that the unique coordination environment of single atom provided by lattice confinement is promising to boost the activity of SACs.
文摘In this work,the tunable introduction of oxygen vacancies in bismuth tungstate was realized via asimple solvothermal method with the assistance of iodine doping.With the predictions afforded bytheoretical calculations,the as-prepared bismuth tungstate was characterized using various tech-niques,such as X-ray diffraction,Raman spectroscopy,scanning electron microscopy,transmissionelectron microscopy,X-ray photoelectron spectroscopy,electron spin resonance spectroscopy,anduV-Vis diffuse reflectance spectroscopy.The different concentrations of the oxygen vacancies onbismuth tungstate were found to be intensely correlated with iodine doping,which weakened thelattice oxygen bonds.Owing to the sufficient oxygen vacancies introduced in bismuth tungstate as aresult of iodine doping,the molecular oxygen activation was remarkably enhanced,thus endowingbismuth tungstate with high activity for the photocatalytic degradation of sodium pentachloro-phenate.More encouraging is the total organic carbon removal rate of sodium pentachlorophenateover iodine-doped bismuth tungstate that exceeded 90%in only 2 h and was 10.6 times higher thanthat of the pristine bismuth tungstate under visible light irradiation.Moreover,the mechanism,through which the degradation of sodium pentachlorophenate over iodine-doped bismuth tung-state is enhanced,was speculated based on the results of radical detection and capture experiments.This work provides a new perspective for the enhanced photocatalytic degradation of organochlo-rine pesticides from the oxygen vacancy-induced molecular oxygen activation over iodine-dopedbismuth tungstate.
基金supported by The Netherlands Organization for Scientific Research(NWO)through a Vici grant and Nuffic fundingfunding from the European Union’s Horizon 2020 research and innovation programme under grant No.686086(Partial-PGMs)。
文摘Density functional theory calculations were carried out to investigate the influence of doping transition metal(TM) ions into the ceria surface on the activation of surface lattice oxygen atoms. For this purpose, the structure and stability of the most stable(111) surface termination of CeO2 modified by TM ions was determined. Except for Zr and Pt dopants that preserve octahedral oxygen coordination, the TM dopants prefer a square-planar coordination when substituting the surface Ce ions. The surface construction from octahedral to square-planar is facile for all TM dopants, except for Pt(1.14 e V) and Zr(square-planar coordination unstable). Typically, the ionic radius of tetravalent TM cations is much smaller than that of Ce4+, resulting a significant tensile-strained lattice and explaining the lowered oxygen vacancy formation energy. Except for Zr, the square-planar structure is the preferred one when one oxygen vacancy is created. Thermodynamic analysis shows that TM-doped CeO2 surfaces contain oxygen defects under typical conditions of environmental catalysis. A case of practical importance is the facile lattice oxygen activation in Zr-doped CeO2(111), which benefits CO oxidation. The findings emphasize the origin of lattice oxygen activation and the preferred location of TM dopants in TM-ceria solid solution catalysts.
基金the National Key Research and Development Program of China(No.2022YFB3803600)the National Natural Science Foundation of China(Nos.52272244 and 51972288)+1 种基金the Fundamental Research Funds for the Central Universities(No.2652022202)2021 Graduate Innovation Fund Project of China University of Geosciences,Beijing(No.ZY2021YC006).
文摘Piezoelectric semiconductors bear the bifunctional photocatalysis and piezocatalysis,while the absent or weak internal charge driving force severely restricts its catalytic activity.Developing polarization strategy is desirable,and particularly understanding its mechanism from a microscopic perspective remains scanty.Herein,we report a secondary recrystallization approach to achieving the simultaneous micro-and macroscopic polarization enhancement on Bi2WO6 nanosheets for boosting piezo-photocatalytic oxygen activation,and unravel the mechanism at an atom-level.The secondary recrystallization process not only results in a strengthened distortion of[WO6]octahedra with distortion index enhancement by~20%for a single octahedron,but also enables lateral crystal growth of nanosheets along the ab plane(av.50 to 180 nm),which separately allows the rise in dipole moment of unit cell(e.g.,1.63 D increase along a axis)and the stacking of the distorted[WO6]octahedron to accumulate the unit cell dipole,collectively contributing to the considerably strengthened spontaneous polarization and piezoelectricity.Besides,exposure of large-area{001}front facet enables more efficient capture and conversion of stress into piezo-potential.Therefore,the well-recrystallized Bi2WO6 nanosheets exhibit considerably promoted piezo-photocatalytic reactive oxygen species generation,given the decreased specific surface area.This work presents a feasible methodology to regulate inside-out polarization for guiding carriers transfer behavior,and may advance the solid understanding on the intrinsic mechanism.
基金the National Natural Science Foundation of China(No.22005306)for financial support。
文摘Using a ditopic organic linker 4-(1H-pyrazol-4-yl)benzoic acid(H_(2)pba),FICN-6,a metal-organic framework containing both Cu_(2)(O_(2)CR)_(4)and Cu_(3)(OH)(pyz)_(3)(O_(2)CR)secondary building units(SBUs),was synthesized.FICN-6 adopts in an unusual intercatenated structure with SBUs from two distinct networks connecting to each other.Presence of Cu_(3)clusters makes FICN-6 a good heterogeneous catalyst for oxygen activation and aerobic oxidative C-C coupling of organic boronic acids.
文摘Selective aerobic oxidation of alcohols under mild conditions is of great importance yet challenging,with the activation of molecular oxygen(O2)as a crucial capability of the catalysts.Herein,we demonstrate that an Al2O3-supported Pd single-atom catalyst leads to higher activity and selectivity compared to Pd nanoparticles for the oxidation of cinnamyl alcohol.The Al2O3 support used in this study is rich in coordinately unsaturated Al3+sites,which are apt for binding to Pd atoms through oxygen bridges and present a distinct metal-support interaction(MSI).The suitable MSI then leads to a unique electronic characteristic of the Pd single atoms,which can be confirmed via X-ray photoelectron spectroscopy,normalized X-ray absorption near-edge structure,and diffuse reflectance Fourier transform infrared spectroscopy.Moreover,this unique electronic state is proposed to be responsible for its high catalytic activity.With the help of in-situ UV-vis spectra and electron spin resonance spectra,a specific alcohol oxidation route with O2 activation mechanism is then identified.Active oxygen species behaving chemically like singlet-O2 are generated from the interaction of O2 with Pd1/Al2O3,and then oxidize the partially dehydrogenated intermediates produced by the adsorbed allylic alcohols and Pd atoms to the desired alkenyl aldehyde.This work provides a promising path for the design and development of high-activity catalysts for aerobic oxidation reactions.
基金the National Natural Science Foundation of China(No.U1862111)Sichuan Science andTechnology Program(No.2020ZDZX0008)+3 种基金Sichuan Provincial International Cooperation Project(No.2019YFH0164)International Collaboration Project of Chengdu City(No.2017-GH02-00014HZ)Graduate Scientific Research Innovation Foundation of SWPU(No.2019cxyb013)Cheung Kong Scholars Programme of China。
文摘Largely limited by the high dissociation energy of the O—O bond,the photocatalytic molecular oxygen activation is highly challenged,which re strains the application of photocatalytic oxidation technology for atmospheric pollutants removal.Herein,we design and fabricate the InP QDs/g-C_(3)N_(4) compounds.The introduction of InP QDs promotes the charge transfer within the interface resulting in the effective separation of photo-generated carriers.Furthermore,InP QDs greatly facilitates the activation of molecular oxygen and promote the formation of O_(2)·under visible-light illuminatio n.These conclusions are identified by experimental and calculation results.Hence,NO can be combined with the O_(2)·to form O—O—N—O intermediate to direct conversion into NO_(3).As a result,the NO removal ratio of g-C_(3)N_(4) has a one fold increase after InP QDs loaded and the generation of NO_(2) is effectively inhibited.This wo rk may provide a strategy to design highly efficient materials for molecular oxygen activation.
基金supported by the National Key R&D Program of China(No.2017YFA0700104)the National Natural Science Foundation of China(Nos.21905204,21931007,and 21790052)111 Project of China(No.D17003).
文摘Sunlight-driven activation of molecular oxygen(O_(2))for organic oxidation reactions offers an appealing strategy to cut down the reliance on fossil fuels in chemical industry,yet it remains a great challenge to simultaneously tailor the charge kinetics and promote reactant chemisorption on semiconductor catalysts for enhanced photocatalytic performance.Herein,we report iron sites immobilized on defective BiOBr nanosheets as an efficient and selective photocatalyst for activation of O_(2) to singlet oxygen(^(1)O_(2)).These Fe^(3+) species anchored by oxygen vacancies can not only facilitate the separation and migration of photogenerated charge carrier,but also serve as active sites for effective adsorption of 02.Moreover,low-temperature phosphorescence spectra combined with X-ray photoelectron spectroscopy(XPS)and electronic paramagnetic resonance(EPR)spectra under illumination reveal that the Fe species can boost the quantum yield of excited triplet state and accelerate the energy transfer from excited triplet state to adsorbed O2 via a chemical loop of Fe^(3+)/Fe^(2+),thereby achieving highly efficient and selective generation of ^(1)O_(2).As a result,the versatile iron sites on defective BiOBr nanosheets contributes to near-unity conversion rate and selectivity in both aerobic oxidative coupling of amines to imines and sulfoxidation of organic sulfides.This work highlights the significant role of metal sites anchored on semiconductors in regulating the charge/energy transfer during the heterogeneous photocatalytic process,and provides a new angle for designing high-performance photocatalysts.
基金financial support by the Program for the Outstanding Innovative Teams of Higher Learning Institutions of Shanxi(OIT)Shanxi Province Hundred Talent Project
文摘In recent decade, Au nanoclusters of atomic precision （AunLm, where L= organic ligand： thiolate andphosphine） have been shown as a new promising nanogold catalyst. The well-defined AunLm catalystspossess unique electronic properties and frameworks, providing an excellent opportunity to correlate theintrinsic catalytic behavior with the cluster＇s framework as well as to study the catalytic mechanismsover gold nanoclusters. In this review, we only demonstrate the important roles of the gold nanoclustersin the oxygen activation （e.g., 302 to 102） and their selective oxidations in the presence of oxygen （e.g., COto C02, sulfides to sulfoxides, alcohol to aldehyde, styrene to styrene epoxide, amines to imines, andglucose to gluconic acid）. The size-specificity （Au25 （1.3 nm）, Au38 （].5 nm）, Au144 （1.9 nm）, etc.）, ligandengineering （e.g., aromatic vs aliphatic）, and doping effects （e.g., copper, silver, palladium, and platinum）are discussed in details. Finally, the proposed reactions＇ mechanism and the relationships of clusters＇structure and activity at the atomic level also are presented.
基金supported by the National Natural Science Foundation of China(No.22108043)Natural Science Foundation of Guangdong Province,China(No.2023A1515012711).
文摘Cobalt-rich perovskite oxides play a paramount role in catalyzing oxygen evolution reaction(OER)on account of their acceptable intrinsic activity but are still challenging due to the high costs and undesired stability.In response to the defects,herein,the Mg-incorporated perovskite cobaltite SrCo_(0.6)Fe_(0.3M)g_(0.1)O_(3-δ)(SCFM-0.1)is proposed as a novel earth-abundant and durable OER electrocatalyst.A well-consolidated cubic-symmetry structure and more active oxygen intermediates are enabled upon Mg substitution.Hence,the optimized SCFM-0.1 perovskite oxide achieves prominent OER electrocatalytic performance,that is,a low overpotential of only 320 mV at 10 mA cm^(-2),a small Tafel slope of 65 mV dec^(-1),as well as an outstanding durability within 20 h,substantially outperforming that of the pristine SrCo_(0.7)Fe_(0.3)O_(3-δ)and benchmark Ba_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3-δ)and IrO_(2) catalysts.The strong pHdependent behavior associated with lattice oxygen activation mechanism for SCFM-0.1 catalyst is also confirmed.This work paves a unique avenue to develop cost-effective and robust perovskite cobaltites for efficient OER electrocatalysis.
文摘<img src="Edit_bdc7d851-e537-40df-990c-d678defa9648.png" alt="" />(M = Au, Ag, Cu;<span lang="EN-US" style="font-size:9pt;font-family:"color:black;"><i>n</i></span>= 1, 2, 3) clusters were used as a cluster model to study the activation of oxygen molecules on single-atom catalysts. Structures of <img src="Edit_bb84deb7-e24a-4777-a2f6-a1621ddd2afc.png" alt="" /> clusters were studied by density functional calculations with global optimization. For each <span style="font-family:"color:black;white-space:normal;"><i>n</i></span>, the most stable structures are quite similar for different metal types, and the oxygen molecule prefers to be adsorbed onto M atoms. It is found that the activation degree of oxygen is higher on clusters with non-noble metal Cu than that of Ag or Au containing clusters, by comparing the changes of O-O bond length and vibrational frequency, natural charge population analysis, Fuzzy bond order analysis, and energy barriers of O<sub>2</sub> dissociation. CO oxidation was used as a probe reaction to study the reactivity of Cu-containing clusters, and it is found that the reactivity decreases with the increase of the size of silicon-oxygen clusters. Our results give a new aspect to understand the reaction mechanism of non-precious metal single-atom catalyst for oxygen activation with high efficiency.
基金supported by the National Key Research and Development Program of China (Project No.2018YFB1502903)。
文摘Metal-based perovskite oxides have contributed significantly to the advanced oxidation processes(AOPs)due to their diverse active sites and excellent compositional/structural flexibility.In this study,we specially designed a perovskite oxide with abundant oxygen vacancies,SrCo_(0.8)Fe_(0.2)O_(3)(SCF),and firstly applied it as a catalyst in peroxymonosulfate(PMS) activation towards organic pollutants degradation.The result revealed that the prepared SCF catalyst exhibited excellent performance on organic compounds degradation.Besides,SCF showed much better activity than La_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3)(LSCF) in terms of reaction rate and stability for the degradation of the organic compounds.Based on the analysis of scanning electron microscope,transmission electron microscope,X-ray diffraction,N_(2) adsorption-desorption,X-ray photoelectron spectroscopy and electron paramagnetic resonance,it was confirmed that the perovskite catalysts with high content of Sr doping at A-site could effectively create a defect-rich surface and optimize its physicochemical properties,which was responsible for the excellent heterogeneous catalytic activity of SCF.SCF can generate three highly active species:~1 O_(2),SO_(4)^(-)· and ·OH in PMS activation,revealing the degradation process of organic compounds was a coupled multiple active species in both radical and nonradical pathway.Moreover,it was mainly in a radical pathway in the degradation through PMS activation on SCF and SO_(4)^(-)· radicals produced were the dominant species in SCF/PMS system.This study demonstrated that perovskite-type catalysts could enrich OVs efficiently by doping strategy and regulate the PMS activation towards sulfate radical-based AOPs.
基金supported by the National Natural Science Foundation of China(52261145701 and U21A20162)the 2115 Talent Development Program of China Agricultural University.
文摘The function-led design of porous hydrochar from mineral-rich biowaste for environmental applications inevitably suffers from carbon-ash recalcitrance.However,a method to alter the original carbon skeleton with ash remains elusive and hinders the availability of hydrochar.Herein,we propose a facile strategy for breaking the rigid structure of carbon-ash coupled hydrochar using phase-tunable molten carbonates.A case system was designed in which livestock manure and NaHCO3 were used to prepare the activated hydrochar,and NH3 served as the target contaminant.Due to the redox effect,we found that organic fractions significantly advanced the melting temperature of Na2CO3 below 800℃.The Na species steadily broke the carbon-ash interaction as the thermal intensity increased and transformed inorganic constituents to facilitate ash dissolution,rebuilding the hydrochar skeleton with abundant hierarchical channels and active defect edges.The surface polarity and mesopore distribution collectively governed the five cycles NH3 adsorption attenuation process.Manure hydrochar delivered favorable potential for application with a maximum overall adsorption capacity of 100.49 mg·g^(-1).Integrated spectroscopic characterization and theoretical computations revealed that incorporating NH3 on the carbon surface could transfer electrons to chemisorbed oxygen,which promoted the oxidation of pyridine-N during adsorption.This work offers deep insight into the structure function correlation of hydrochar and inspires a more rational design of engineered hydrochar from high-ash biowaste.
文摘During the course of mungbean (Phaseolus radiatus L.) germination, the rate of ethylene production and the activity of ACC synthase (1_aminocyclopropane_1_carboxylic acid synthase, EC4.4.1.4) began to increase in the 5th day of germination, and reached its peak in the 10th day and then decreased. The ethylene production and the activity of ACC synthase were obviously promoted by 10 μmol/L exogenous IAA (indole_3_acetic acid). The production of superoxide radical (O -· 2) and hydrogen peroxide (H 2O 2) were also promoted by exogenous IAA, suggesting that there was some relationship between active oxygen production and the activity of ACC synthase induced by exogenous IAA. The production of ethylene and the activity of ACC synthase increased dramatically when the seedlings were treated with exogenous O -· 2, whereas the exogenous H 2O 2 had no effects on the production of ethylene and the activity of ACC synthase. Exogenous SOD (superoxide dismutase, one scavenger of O -· 2) could inhibit the production of ethylene and the activity of ACC synthase, but exogenous CAT (catalase) could not. So it was possible that IAA would stimulate the activity of ACC synthase by inducing the production of O -· 2 in germinating mungbean seedlings, and this might be one of the regulating mechanism of ethylene synthesis in higher plants; the production of H 2O 2 induced by IAA was not the cause of the increase of the activity of ACC synthase and the production of ethylene.
文摘In order to understand the role of active oxygen species in mediating plant injuries induced by far-UV radiation, seedlings of Taxus cuspidata Sieb. et Zucc. were irradiated by far-UV rays in laboratory for 4 weeks. The production of organic free-radicals in detached needles, and the production of O-2(radical anion) and O-1(2) in isolated chloroplasts were detected weekly by electron spin resonance (ESR) to evaluate their relative importance. The results show that the cumulative effect of far-UV irradiation, is best indicated by the production of organic free radicals in the needles, O-2(radical anion) production in chloroplasts is the next. The enhancement of O-1(2) production in chloroplasts by the cumulative far-UV irradiation seems to be not so important as O-2(radical anion) in mediating injuries induced by, far-UV radiation because of its high background value.
文摘[Objective] The research aimed to study the effects of 1-methylcyclopropene （1-MCP） and chitosan on active oxygen metabolism and quality of fresh-cut potato during storage. [Method] The fresh-cut potato slices were respectively treated with 1- MCP （2 μl/L）, chitosan or 1-MCP ＋ chitosan. During the storage period, the contents of superoxide anion （02）, malondialdehyde （MDA）, hydrogen dioxide （H202） and Vita- min C （Vc）, the activities of polyphenol oxidase （PPO）, peroxydase （POD） and super- oxide dismutase （SOD） as well as the respiratory rate of the fresh-cut potatoes in all the treatments were determined every day. The fresh-cut potato slices treated without any reagents were used as control. [Result] 1-MCP Treated could significantly de- creased the respiratory rate, PPO activity and the accumulations of 02 , H202 and MDA, increased the activities of SOD and POD and slowed down Vc content reduc- tion. On the contrary, potato treated with chitosan significantly inhibited the POD activi- ty in fresh-cut potato. Compared with the control, the combination of 1-MCP and chi- tosan showed a little but not significant better effects on potato preservation. [Conclu- sion] 1-MCP Treated showed the best effects on potato preservation.
基金funded by the National Natural Science Fundation of China (30840016)the Natural Science Fundation of Jiangsu Province, China (BK 2010310)the Natural Science Fundation for Colleges and Universities in Jiangsu Province, China (10KJB550004)
文摘Peach fruits [Prumus persica （L.） Batsch, cv. Yuhuasanhao] were used as materials to investigate the changes of reactive oxygen species （ROS） and related enzymes in mitochondria respiration during storage and then their influence on senescence of harvested Peach fruits was studied. The results showed that low temperature （5℃） strongly inhibited the reduction of firmness and the increase in respiration rate. During storage at ambient temperature （20℃）, ROS had a cumulative process while malondialdehye （MDA） content continued to increase in associated with enhanced membrane lipid peroxidation. Lipoxygenase （LOX） activity was strongly inhibited under the low temperature condition. The activities of succinic dehydrogenase （SDH）, cytochrome C oxidase （CCO）, and Ca^2＋-ATPase declined to a certain extent at ambient temperature, while they showed higher activities at low temperature, which may be related to lower membrane lipid peroxidation at low temperature. Higher Ca^2＋ content at ambient temperature may be responsible for impairment of mitochondrial function, thus, leading to fruit senescence. The results showed that under low temperature condition, the low accumulation of ROS and the low level of membrane lipid peroxidation could maintain the function of mitochondria that would help to delay the senescence of peach fruits. These suggested a close relationship existed between ROS metabolism and mitochondrial respiration. It can be inferred that the low temperature helps to delay senescence of peach fruits via suppression of ROS and related enzymes, maintain better homeostasis of Ca^2＋ in mitochondria and thus better mitochondrial functions.
基金This work is supported by Collaborative Innovation Center of Suzhou Nano Science and Technology, Ministry of Science and Technology of China （No.2014CB932700）, the National Natural Science Foundation of China （No.21603208, No.21573206, and No.51371164）, the China Postdoctoral Science Foundation （No.2015M580536, No.2016T90569）, Key Research Program of Frontier Sciences, CAS （QYZDBSSW- SLH017）, Strategic Priority Research Program B of the CAS （No.XDB01020000）, Hefei Science Center, CAS （No.2015HSC-UP016）, and Fundamental Research Funds for the Central Universities.
文摘Pt-based nanoframes represent a class of promising catalysts towards oxygen reduction reaction. Herein, we, for the first time, successfully prepared Pt-Pd octahedral nanoframes with ultrathin ridges less than 2 nm in thickness. The Pt-Pd octahedral nanoframes were obtained through site-selected deposition of Pt atoms onto the edge sites of Pd octahedral seeds, followed by selective removal of the Pd octahedral cores via chemical etching. Due to that a combination of three-dimensional opens geometrical structure and Pt-skin surface compositional structure, the Pt-Pd octahedral nanoframes/C catalyst shows a mass activity of 1.15 A/mgPt towards oxygen reduction reaction, 5.8 times enhancement in mass activity relative to commercial Pt/C catalyst （0.20 A/mgPt）. Moreover, even after 8000 cycles of accelerated durability test, the Pt-Pd octahedral nanoframes/C catalyst still exhibits a mass activity which is more than three times higher than that of pristine Pt/C catalyst.
